U.S. Pat. No. 2,879,306 discloses the hydrogenation of butadienepolyperoxide over palladium, nickel, rhodium, cobalt and platinum. A second stage hydrogenation over copper chromite, molybdenum sulfide and nickel is also disclosed. The resulting product is a mixture of 1,4-butanediol and 1,2-butanediol. The 1,2-butanediol is not used commercially and therefore is less valuable than the 1,4-butanediol.
Handy and Rothrock in J. American Chemical Society, 80, 5306 disclose the hydrogenation of butadienepolyperoxide in a silver-lined reactor over palladium followed by hydrogenation over ruthenium. The products were 2-hydroxybutanal, 1,2-butanediol and 1,4-butanediol.
British Pat. No. 1,018,661 discloses the hydrogenation of unsaturated organic hydroperoxides over modified palladium or platinum catalysts to give unsaturated alcohols. Modifiers disclosed include silver. An improvement in the amount of hydroperoxides reduced is shown with the modified catalysts.
Japanese Pat. Nos. 096,634 and 087,126 disclose the hydrogenation of butadieneperoxide polymer over Raney nickel to give 1,2- and 1,4-butanediol.
U.S. Pat. No. 4,002,692 discloses the hydrogenation of polymeric butadieneperoxide over a nickel catalyst to prepare 1,2- and 1,4-butanediol.
The reduction of butadienepolyperoxide to butanediols in the prior art gives maximum yields of the desired 1,4-butanediol of about 50% with a 20-30% yield of the commercially unattractive 1,2-butanediol. The reduction is carried out using a catalyst which rapidly becomes inactivated by contact with the peroxide and must be regenerated frequently. The reduction is very exothermic and is usually done stepwise under successively more severe conditions until reduction is complete.
The preparation of 1,4-butanediol is important not only for uses as solvents and monomers for the preparation of polyesters but also for use in the preparation of tetrahydrofuran.
The preparation of 1,4-butanediol by condensation of formaldehyde and acetylene to 2-butyne-1,4-diol followed by reduction to 1,4-butanediol is another process well known in the art and is a process that is practiced commercially. However, because of the escalating cost of acetylene, this process may rapidly become uneconomical.
Also described in the art is the oxidation of butane or benzene to maleic anhydride followed by reduction to butanediol or tetrahydrofuran.